CN101302622B - Method for preparing hexahydric alcohol by saccharose electrolytic reduction - Google Patents
Method for preparing hexahydric alcohol by saccharose electrolytic reduction Download PDFInfo
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- CN101302622B CN101302622B CN200810073432.XA CN200810073432A CN101302622B CN 101302622 B CN101302622 B CN 101302622B CN 200810073432 A CN200810073432 A CN 200810073432A CN 101302622 B CN101302622 B CN 101302622B
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- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 title claims abstract description 42
- 229930006000 Sucrose Natural products 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 23
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 title claims abstract description 6
- 229960004793 sucrose Drugs 0.000 title claims description 38
- 230000009467 reduction Effects 0.000 title claims description 6
- 235000013681 dietary sucrose Nutrition 0.000 title claims description 3
- 239000005720 sucrose Substances 0.000 claims abstract description 38
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 32
- 239000007788 liquid Substances 0.000 claims abstract description 30
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 claims abstract description 27
- 229930195725 Mannitol Natural products 0.000 claims abstract description 27
- 239000000594 mannitol Substances 0.000 claims abstract description 27
- 235000010355 mannitol Nutrition 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- 230000008569 process Effects 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims description 22
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- 230000007062 hydrolysis Effects 0.000 claims description 13
- 238000006460 hydrolysis reaction Methods 0.000 claims description 13
- MEIRRNXMZYDVDW-MQQKCMAXSA-N (2E,4E)-2,4-hexadien-1-ol Chemical group C\C=C\C=C\CO MEIRRNXMZYDVDW-MQQKCMAXSA-N 0.000 claims description 12
- 238000002425 crystallisation Methods 0.000 claims description 11
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 10
- 229910000564 Raney nickel Inorganic materials 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- 239000008103 glucose Substances 0.000 claims description 10
- 238000005303 weighing Methods 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 9
- 229930091371 Fructose Natural products 0.000 claims description 8
- 239000005715 Fructose Substances 0.000 claims description 8
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 239000008151 electrolyte solution Substances 0.000 claims description 8
- 230000005611 electricity Effects 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 230000008025 crystallization Effects 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000012452 mother liquor Substances 0.000 claims description 5
- 229910001220 stainless steel Inorganic materials 0.000 claims description 5
- 239000010935 stainless steel Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 4
- 238000010790 dilution Methods 0.000 claims description 4
- 239000012895 dilution Substances 0.000 claims description 4
- 239000012153 distilled water Substances 0.000 claims description 4
- 238000001953 recrystallisation Methods 0.000 claims description 4
- 239000000706 filtrate Substances 0.000 claims description 3
- 238000005903 acid hydrolysis reaction Methods 0.000 claims description 2
- 230000003301 hydrolyzing effect Effects 0.000 claims description 2
- 238000012546 transfer Methods 0.000 claims description 2
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000003344 environmental pollutant Substances 0.000 abstract description 2
- 231100000719 pollutant Toxicity 0.000 abstract description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 abstract 1
- 239000000600 sorbitol Substances 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 150000004678 hydrides Chemical class 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 6
- 239000001117 sulphuric acid Substances 0.000 description 6
- 235000011149 sulphuric acid Nutrition 0.000 description 6
- 230000001186 cumulative effect Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 230000009466 transformation Effects 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- WQZGKKKJIJFFOK-PQMKYFCFSA-N alpha-D-mannose Chemical compound OC[C@H]1O[C@H](O)[C@@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-PQMKYFCFSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000004904 shortening Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 235000000346 sugar Nutrition 0.000 description 2
- 229940034610 toothpaste Drugs 0.000 description 2
- 239000000606 toothpaste Substances 0.000 description 2
- AOFUBOWZWQFQJU-SNOJBQEQSA-N (2r,3s,4s,5r)-2,5-bis(hydroxymethyl)oxolane-2,3,4-triol;(2s,3r,4s,5s,6r)-6-(hydroxymethyl)oxane-2,3,4,5-tetrol Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O.OC[C@H]1O[C@H](O)[C@H](O)[C@@H](O)[C@@H]1O AOFUBOWZWQFQJU-SNOJBQEQSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 241000208125 Nicotiana Species 0.000 description 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000003005 anticarcinogenic agent Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 230000002490 cerebral effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000002934 diuretic Substances 0.000 description 1
- 230000001882 diuretic effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229940021013 electrolyte solution Drugs 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000006345 epimerization reaction Methods 0.000 description 1
- 235000021433 fructose syrup Nutrition 0.000 description 1
- ICJBPZBRDLONIF-UHFFFAOYSA-N hexane-1,1,1,2,2,3-hexol Chemical compound CCCC(O)C(O)(O)C(O)(O)O ICJBPZBRDLONIF-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003978 infusion fluid Substances 0.000 description 1
- 230000004410 intraocular pressure Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 235000019154 vitamin C Nutrition 0.000 description 1
- 239000011718 vitamin C Substances 0.000 description 1
Landscapes
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a method of preparing hexahydric alcohol with sucrose as raw material by electrolysis. The method uses the common edible sucrose as the raw material to be hydrolyzed under certain conditions; after simple pretreatment, the sucrose is put into an electrolyzer, electrolyzed and hydrogenated in the presence of catalyst; mother liquid is filtered, concentrated, crystallized, separated and purified for preparing the hexahydric alcohol, and then two products comprising mannitol and sorbitol are obtained. The method is simple in process, emits no pollutant in production process, has the products which is easy to be separated, and has the hydrogenation conversion rate over 95 percent.
Description
Technical field:
The present invention relates to a kind of is raw material with sucrose, produces the method for hexavalent alcohol (N.F,USP MANNITOL and sorbyl alcohol) by electrolysis.
Background technology:
Hexavalent alcohol is a hexan-hexol, and molecular formula is C
6H
14O
6, comprise N.F,USP MANNITOL and sorbyl alcohol.Sorbyl alcohol and N.F,USP MANNITOL are two kinds of isomeric hexitols, and is of many uses, and they all can be used to control surface promoting agent, tackiness agent, softening agent and are used as foodstuff additive.Sorbyl alcohol also is used for industries such as toothpaste, makeup, tobacco, vitamins C; N.F,USP MANNITOL also is used to produce diuretic(s), cerebral and intraocular pressure depressor and amino acid is made compound infusion solution and synthetic anticarcinogen etc.
At present, generally all adopt glucose chemistry catalytic hydrogenation to make inside and outside the producing country of sorbyl alcohol; N.F,USP MANNITOL can extract from sea-tangle, or is that the catalytic material hydrogenation makes with sucrose hydrolysis liquid, or be raw material with glucose through enzyme partly change into fructose, seminose again shortening make.Domestic N.F,USP MANNITOL mainly is to be that raw material extracts with the sea-tangle, has refining formality trouble, and yield is low, and quality product is bad, many shortcomings such as production cost height, and the chemical catalysis hydrogenation is also because of being subjected to the equipment requirements height, the hydrogen limited popularization that restricts technology in source.
The sucrochemistry shortening is prepared N.F,USP MANNITOL technology, and Nanning city chemical research designing institute has carried out a lot of researchs.CN1528916A is a raw material with edible sucrose or white sugar, through chemical treatment and separation, and the technology of high yield combined production of crystallized fructose and crystallized mannitol product, the yield of two kinds of products adds up to 70% (by the charging capacity of sucrose).CN1687432 and CN1686987 are raw material with sucrose, hydrolysis after simulation moving-bed resulting separation be rich in the glucose component, be rich in glucose component recirculation and carry out epimerization reaction, be rich in the fructose component and carry out hydrogenation reaction, make with this method and to be rich in the fructose component and to be rich in the glucose component and all to have obtained effective utilization, thereby make the yield of N.F,USP MANNITOL can reach 42%, obviously improved productivity effect.
Adopt electrolysis hydrogenation sucrose to produce hexavalent alcohol, domesticly also carried out some researchs.Hebei Normal University turns round and look to step on to put down at works " organic electrosynthesis progress " and " fine chemistry industry " 2000 the 10th phases and adopts electrolysis hydrogenation sucrose or glucose to prepare N.F,USP MANNITOL and sorbyl alcohol, and the transformation efficiency of sugar is 74%-86%; " fine chemistry industry " 2003 11 phases and " toothpaste industry " first phase in 2004 report that respectively the Liu Yan of Hebei Normal University spring etc. makes raw material with sucrose, generate Nulomoline (glucose of equivalent and fructose) through hydrolysis, change into the mixture of glucose, fructose, seminose again through ammonium molybdate.Raney Ni powder electrode is done negative electrode, PbO
2/ Ti electrode is done anode, and electrolytic reduction is produced N.F,USP MANNITOL, sorbyl alcohol in diaphragm sell, has determined that optimum process condition is: total sugar concentration 0.50mol/L, current density 3.0A/dm
2, pH=9, e=35 ℃, energising amount 1.3F/mol, transformation efficiency can reach 84%.The Hu Zhongyu of Nanchang higher junior college etc. is raw material at " Nanchang high commissioner journal " report with rich fructose syrup in addition, makes medicinal N.F,USP MANNITOL with the method for electrochemical reduction, and sugared transformation efficiency reaches 80.3%.Generally speaking, the problem that electrochemical reduction technology exists is that transformation efficiency is not high, and peak rate of conversion is 86% in the report, has caused reaction back product and unreacting material to mix, and it is difficult to separate, and the product impurity that obtains is many, of poor quality, and raw material consumption is also high simultaneously.
Summary of the invention
The purpose of this invention is to provide a kind of the deficiencies in the prior art part that can overcome, sucrose inversion is N.F,USP MANNITOL and sorbyl alcohol height, energy consumption is lower, production technique is simple, is raw material with sucrose, produce the method for hexavalent alcohol by electrolysis.
Method is as follows: at first sucrose is added the hydrolyzed solution that the appropriate hydrochloric acid hydrolysis treatment generates fructose and glucose, take by weighing quantitative sucrose hydrolysis liquid again, add Raney's nickel as catalyzer, be made into cathode solution, other joins an amount of dilution heat of sulfuric acid is electrolytic anode liquid, squeeze into tank room circulation carrying out electrolysis separately with pump respectively, filtering separation catalyzer, filtrate obtain the thick N.F,USP MANNITOL of crystallization through decolouring, crystallisation by cooling, filtering separation, recrystallization obtains pharmaceutical grade N.F,USP MANNITOL, and mother liquor is a sorbyl alcohol.Reaction formula is:
Above-described hydrolytic process is that heating makes its dissolving in the reactor that edible sucrose and distilled water are stirred with 1: 1 ratio input band, and adds appropriate hydrochloric acid and transfer PH to 2-4, continue heating then, maintenance 2-4 hour is stirred in 70-100 ℃ of temperature control, cools off standby.
Above-described electrolytic process is to take by weighing quantitatively above sucrose hydrolysis liquid, add Raney's nickel as catalyzer, consumption is the 20-40% of charging capacity, be made into cathode solution, other joins an amount of dilution heat of sulfuric acid is electrolytic anode liquid, squeeze into tank room circulation separately with pump respectively and carry out electrolysis, the electrolytic process controlled temperature is 30-50 ℃, electrolytic current density 2.4-4A/dm
2, electrolytic solution PH7-10, when electrolysis electricity when being 1.1-1.5 times of theoretical electric weight reaction can finish, the electrolysis hydride conversion rate is greater than 95%.
Above-described electrolytic process is to leave standstill the after-filtration separating liquiding catalyst after the material hydrogenation, filtrate is used activated carbon decolorizing, solution exchanges through male-female ion exchange resin, to remove the pigment that remaining catalyzer and reaction generate, solution moves into rotatory evaporator then, be concentrated into 60-70% concentration, elder generation's naturally cooling, add the small amount of mannitol crystal seed, put into the refrigerator crystallisation by cooling, temperature is controlled at 0-10 ℃, time 16-24 hour, last filtering separation, crystallization is thick N.F,USP MANNITOL, mother liquor is the technical grade sorbyl alcohol.
Above-described decolouring, crystallisation by cooling, filtering separation process are the thick N.F,USP MANNITOL adding of above-mentioned crystalline first time distilled water to be made into 40-60% concentration solution carry out the crystallization second time, crystallization condition is identical, recirculation was used when filtering separation then, filtrated stock stayed time aftertreatment.Crystal is dried 90-100 ℃ of temperature, promptly obtains technical grade N.F,USP MANNITOL.Technical grade N.F,USP MANNITOL is carried out recrystallization can obtain pharmaceutical grade N.F,USP MANNITOL.
Nucleus equipment of the present invention mainly is an electrolyzer, and the material that anode electrolytic cell adopts comprises carbon, lead, PbO
2/ Ti etc., the material that negative electrode adopts comprises iron, stainless steel, nickel etc., and electrolyzer is divided into anolyte compartment and cathode compartment with cationic membrane, and the anolyte compartment adds dilute sulphuric acid or the circulation of other electrolyte solutions, and cathode compartment adds treated sucrose solution circulation.
The method of producing hexavalent alcohol of the present invention, the Raney's nickel catalyst of hydrogenation can recirculation use, and access times are more than 40 times under the prerequisite that guarantees reaction yield.
Advantage of the present invention is to utilize electrolysis rather than chemical hydrogenation, can avoid chemical catalysis equipment requirements height, shortcomings such as the hydrogen source is restricted simultaneously by technology is improved, make sucrose electrolysis hydride conversion rate be higher than the research level of present report, average hydride conversion rate is greater than 95%, generally reach 98%, make and react back product separate easily, the good product quality that obtains after the crystallization, whole Technology has reached industrialization demands, and non-pollutant discharge.It is big that Technology can have been given full play to the southern area sucrose yield, and the advantage that electric power resource is abundant is for Reprocessing of sucrose provides a kind of extraordinary approach.
Embodiment
Describe in detail below in conjunction with embodiment.
Example 1:
Take by weighing the 2000g edible sucrose and put into there-necked flask, add 2000ml distilled water, add an amount of dilute hydrochloric acid, heating in water bath stirs, and 80 ℃ of constant temperature 3 hours are regulated PH to neutral with NaOH after naturally cooling to 50-60 ℃, with small amount of activated solution is decoloured, obtain mother liquor 3956.4g after the filtration, the sucrose hydrolysis transformation efficiency is 98.2% by analysis, cools off standby.
Example 2:
Take by weighing example 1 gained sucrose hydrolysis liquid 684.6g (being equivalent to 1mol sucrose), add the 400g Raney's nickel catalyst, being made into cumulative volume is that 1000ml solution is as electrolysis cathode liquid, other joins 800ml concentration is that the sulphuric acid soln of 1ml/L is an electrolytic anode liquid, electrolytic solution is squeezed in the anolyte compartment and cathode compartment of electrolyzer with the pump circulation respectively, anode electrolytic cell adopts plumbous, and negative electrode adopts stainless steel, and electrolytic condition is: current density 3.2A/dm
2, electrolysis electricity is 140Ah, electrolysis temperature 35-40 ℃, reaction process uses dilute NaOH solution control cathode liquid PH at 8-9; It is 98.5% that reaction finishes to analyze hydride conversion rate, and catalyzer stays time experiment and recycles.
Example 3:
Take by weighing example 1 gained sucrose hydrolysis liquid 684.6g (being equivalent to 1mol sucrose), add the 400g Raney's nickel catalyst, being made into cumulative volume is that 1000ml solution is as electrolysis cathode liquid, other joins 800ml concentration is that the sulphuric acid soln of 1ml/L is an electrolytic anode liquid, electrolytic solution is squeezed in the anolyte compartment and cathode compartment of electrolyzer with the pump circulation respectively, and anode electrolytic cell adopts PbO
2/ Ti, negative electrode adopts stainless steel, and electrolytic condition is: current density 3.2A/dm
2, electrolysis electricity is 140Ah, electrolysis temperature 45-50 ℃, reaction process uses dilute NaOH solution control cathode liquid PH at 8-9; It is 98.1% that reaction finishes to analyze hydride conversion rate, and catalyzer stays time experiment and recycles.
Example 4:
Take by weighing example 1 gained sucrose hydrolysis liquid 684.6g (being equivalent to 1mol sucrose), add the 400g Raney's nickel catalyst, being made into cumulative volume is that 1000ml solution is as electrolysis cathode liquid, other joins 800ml concentration is that the sulphuric acid soln of 1ml/L is an electrolytic anode liquid, electrolytic solution is squeezed in the anolyte compartment and cathode compartment of electrolyzer with the pump circulation respectively, and anode electrolytic cell adopts PbO
2/ Ti, negative electrode adopts stainless steel, and electrolytic condition is: current density 3.2A/dm
2, electrolysis electricity is 140Ah, electrolysis temperature 35-40 ℃, reaction process uses dilute NaOH solution control cathode liquid PH at 10-11; It is 99.0% that reaction finishes to analyze hydride conversion rate, and catalyzer stays time experiment and recycles.
Example 5: take by weighing example 1 gained sucrose hydrolysis liquid 684.6g (being equivalent to 1mol sucrose), add the 400g Raney's nickel catalyst, being made into cumulative volume is that 1000ml solution is as electrolysis cathode liquid, other joins 800ml concentration is that the sulphuric acid soln of 1ml/L is an electrolytic anode liquid, electrolytic solution is squeezed in the anolyte compartment and cathode compartment of electrolyzer with the pump circulation respectively, anode electrolytic cell adopts plumbous, and negative electrode adopts iron, and electrolytic condition is: current density 3.2A/dm
2, electrolysis electricity is 140Ah, 3540 ℃ of electrolysis temperatures, and reaction process uses dilute NaOH solution control cathode liquid PH at 9-10; It is 97.3% that reaction finishes to analyze hydride conversion rate, and catalyzer stays time experiment and recycles.
Example 6: take by weighing example 1 gained sucrose hydrolysis liquid 684.6g (being equivalent to 1mol sucrose), add the 400g Raney's nickel catalyst, being made into cumulative volume is that 1000ml solution is as electrolysis cathode liquid, other joins 800ml concentration is that the sulphuric acid soln of 1ml/L is an electrolytic anode liquid, electrolytic solution is squeezed in the anolyte compartment and cathode compartment of electrolyzer with the pump circulation respectively, anode electrolytic cell adopts carbon, and negative electrode adopts nickel, and electrolytic condition is: current density 3.2A/dm
2, electrolysis electricity is 140Ah, electrolysis temperature 35-40 ℃, reaction process uses dilute NaOH solution control cathode liquid PH at 8-9; It is 97.1% that reaction finishes to analyze hydride conversion rate, and catalyzer stays time experiment and recycles.
Example 7:
Experiment 2,3,4,5, the 6 electrolysis hydrides that obtain merge together, adopt male-female ion exchange resin to purify, again with Rotary Evaporators with solution concentration to 60-70% concentration, add the small amount of mannitol crystal seed behind the naturally cooling, put into the refrigerator crystallisation by cooling then, temperature is controlled at 5 ℃, 24 hours time, filtering separation, mother liquor is the technical grade sorbyl alcohol, the 462.1g that weighs after the solid oven dry, and mannitol content 91.2% by analysis, solid obtains technical grade N.F,USP MANNITOL after the recrystallization oven dry, content is 96.5%.
Claims (1)
1. the method for a preparing hexahydric alcohol by saccharose electrolytic reduction, be to be raw material with sucrose, produce the method for hexavalent alcohol by electrolysis, it is characterized in that: its processing step is as follows: at first sucrose is added the hydrolyzed solution that the appropriate hydrochloric acid hydrolysis treatment generates fructose and glucose, take by weighing quantitative sucrose hydrolysis liquid again, add Raney's nickel as catalyzer, be made into cathode solution, other joins an amount of dilution heat of sulfuric acid is electrolytic anode liquid, squeeze into tank room circulation carrying out electrolysis separately with pump respectively, anode electrolytic cell adopts plumbous, and negative electrode adopts stainless steel, electrolysis after-filtration separating catalyst, filtrate is through decolouring, crystallisation by cooling, filtering separation, obtain the thick N.F,USP MANNITOL of crystallization, recrystallization obtains pharmaceutical grade N.F,USP MANNITOL, and mother liquor is a sorbyl alcohol;
Described hydrolytic process is that heating makes its dissolving in the reactor that edible sucrose and distilled water are stirred with 1: 1 ratio input band, and adds appropriate hydrochloric acid and transfer PH to 2-4, continues heating then, and 70-100 ℃ of temperature control is stirred and kept 2-4 hour, cools off standby;
Described electrolytic process is to take by weighing quantitatively above sucrose hydrolysis liquid, add Raney's nickel as catalyzer, consumption is the 20-40% of charging capacity, be made into cathode solution, other joins an amount of dilution heat of sulfuric acid is electrolytic anode liquid, electrolysis is carried out in circulation in tank room, and the electrolytic process controlled temperature is 30-50 ℃, electrolytic current density 2.4-4A/dm
2, electrolytic solution PH7-10, when electrolysis electricity when being 1.1-1.5 times of theoretical electric weight reaction can finish.
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| CN200810073432.XA CN101302622B (en) | 2008-01-22 | 2008-01-22 | Method for preparing hexahydric alcohol by saccharose electrolytic reduction |
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| CN101884611B (en) * | 2009-12-03 | 2012-01-18 | 四川海思科制药有限公司 | Method for preparing medicinal invert sugar by sugar hydrolysis |
| CN102826785A (en) * | 2012-09-17 | 2012-12-19 | 同济大学 | Method for preparing modified cement grinding aid component material |
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